U.S. patent application number 15/122800 was filed with the patent office on 2017-03-16 for separator for batteries and method for manufacturing the same.
The applicant listed for this patent is AZA HOLDING PTE. LTD. Invention is credited to Didier GUILLONNET, Suren MARTIROSYAN.
Application Number | 20170077556 15/122800 |
Document ID | / |
Family ID | 53525212 |
Filed Date | 2017-03-16 |
United States Patent
Application |
20170077556 |
Kind Code |
A1 |
GUILLONNET; Didier ; et
al. |
March 16, 2017 |
SEPARATOR FOR BATTERIES AND METHOD FOR MANUFACTURING THE SAME
Abstract
A separator which is permeable to hydroxide ion--contains at
least one Dendrite Stopping Substance such as Ni(OH)2, or its
precursor.
Inventors: |
GUILLONNET; Didier; (PARIS,
FR) ; MARTIROSYAN; Suren; (Yerevan, AM) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
AZA HOLDING PTE. LTD |
Singapore |
|
SG |
|
|
Family ID: |
53525212 |
Appl. No.: |
15/122800 |
Filed: |
February 27, 2015 |
PCT Filed: |
February 27, 2015 |
PCT NO: |
PCT/IB2015/051471 |
371 Date: |
August 31, 2016 |
Related U.S. Patent Documents
|
|
|
|
|
|
Application
Number |
Filing Date |
Patent Number |
|
|
61947327 |
Mar 3, 2014 |
|
|
|
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
H01M 10/30 20130101;
H01M 2/14 20130101; Y02E 60/10 20130101; H01M 2/166 20130101; H01M
2220/20 20130101; H01M 10/32 20130101; H01M 2/145 20130101; H01M
2/1633 20130101; H01M 12/08 20130101; H01M 10/24 20130101; H01M
10/34 20130101; H01M 10/4235 20130101 |
International
Class: |
H01M 10/42 20060101
H01M010/42; H01M 10/30 20060101 H01M010/30; H01M 2/16 20060101
H01M002/16; H01M 10/32 20060101 H01M010/32; H01M 2/14 20060101
H01M002/14; H01M 12/08 20060101 H01M012/08 |
Claims
1-11. (canceled)
12. A separator which is permeable to hydroxide ion, for use in an
electrically rechargeable electrochemical cell with alkaline
electrolyte between a Zinc electrode and a counter electrode,
wherein: said separator contains at least one Dendrite Stopping
Substance or DSS, said DSS being a metal-containing compound, said
metal chosen from the metals of the group consisting of Pt, Pd, Ni,
Fe and Mn metal, and, said DSS being in a form of particles.
13. The separator according to claim 12, wherein said DSS is
Ni(OH).sub.2 or one of its precursor, such as NiCO.sub.3 or
NiSO.sub.4.
14. The separator according to claim 12, wherein the size of the
DSS particles is below 250 .mu.m.
15. The separator according to claim 12, wherein the thickness of
the separator is from 50 to 1000 .mu.m.
16. An electrically rechargeable battery, with strong alkaline
electrolyte, comprising at least one separator according to claim
12, said separator being placed between a Zinc electrode and a
counter electrode.
17. The electrically rechargeable battery according to claim 16
comprising an air electrode as cathode.
18. The electrically rechargeable battery according to claim 16,
comprising a nickel-oxide or silver electrode as cathode.
19. An electric or hybrid vehicle comprising at least one
electrically rechargeable battery as defined in claim 16.
20. A method for preparing a separator as defined in claim 12,
comprising a step of soaking a porous or fibrous material with a
DSS precursor, and a step of leaving to precipitate DSS particles
within said material.
21. A method for manufacturing a separator having Dendrite Stopping
Substance properties as defined claim 12, comprising a step of
mixing the material used to prepare a separator with DSS particles.
Description
FIELD OF THE INVENTION
[0001] The present application relates to separators for use in
zinc secondary alkaline batteries and method for manufacturing the
same. Moreover the present invention relates to separators
permeable to hydroxide ion, for use in an electrically rechargeable
electrochemical cell with Zinc electrode and alkaline electrolyte,
and a battery comprising said separator.
BACKGROUND OF THE INVENTION
[0002] It is well known that during the electrical charging of a
zinc anode alkaline battery, zinc dendrites are formed, leading to
the perforation of the separator that lays between the zinc anode
and the charging electrode compartments, and therefore to a
short-circuit, rendering the battery completely useless.
[0003] The typical solution is to use a rayon type or polymeric
porous separator (e.g. anionic exchange membrane, polymeric film
made by zirconia/polysulfone, polymeric films, cellulose films,
etc.). Other typical solutions of separators are described in the
paper "Battery Separators" from Pankaj Arora and Zhengming (John)
Zhang published in Chemical Reviews, 2004, Vol. 104, No. 10, pages
4419-4462, herein incorporated by reference in its entirety.
[0004] However these separators are not totally satisfactory
because they are too permeable to zincate ions and zinc dendrites
are still formed and usually perforate the separator in less than
50 cycles.
[0005] One aim of the present patent application is to provide a
solution to improve the characteristics of such separators and
extend their service life.
[0006] Another aim of the invention is to provide a separator that
can greatly enhance its ability to prevent dendrites
perforation.
[0007] The invention relates to a separator which is permeable to
hydroxide ion, for use in an electrically rechargeable
electrochemical cell with alkaline electrolyte between a Zinc
electrode and a counter electrode, wherein: [0008] said separator
containing at least one Dendrite Stopping Substance or DSS, said
DSS being a metal-containing compound such as oxide, hydroxide,
salt, etc . . . , said metal chosen from the metals of the group
consisting of Pt, Pd, Ni, Fe and Mn, and [0009] said DSS being in a
form of particles.
[0010] The inventor noticed that incorporating some "Dendrite
Stopping Substance" (DSS) particles in the separator's material or
pores reduces dendrite formation.
[0011] In the invention "particle" means an aggregate of material
whose size is below 500 .mu.m.
[0012] The separator of the invention is such that during charging,
i.e. when hydroxide ions are flowing from the zinc electrode
towards the counter electrode, the dendrites growing from the Zinc
electrode towards the counter electrode are stopped in their
progression through the separator when they encounter DSS particles
of the said separator.
[0013] Separators according to the invention can be prepared by
including DSS particles within the material of the separator when
it is formed.
[0014] In other words, the DSS particles are added to the commonly
used materials that are used to prepare separators.
[0015] Separators according to the invention can also be prepared
by impregnating, with DSS particles, porous or fibrous typical
material that are used to form separators. Classical
alkaline-stable separators (known in the art) are for instance made
of Polypropylene (PP)/Polyvinyl chloride (PVC), or
Polytetrafluoroethylene (PTFE) or mixtures thereof. An
alkaline-stable microporous separator according to the invention
can be a microporous PVC separator for use in lead-acid batteries
having a 45% to 70% volumetric porosity, a 0.05 .mu.m to 10 .mu.m
pore size and a 0.1 to 1 mm thickness. The above-mentioned
separator that contains the DSS particles can be obtained, for
example, by soaking a classical separator with a DSS precursor,
which results in DSS particles precipitation.
[0016] In an advantageous embodiment, the invention relates to the
separator mentioned above, wherein said DSS is Ni(OH).sub.2 or one
of its precursor, such as NiCO.sub.3 or NiSO.sub.4.
[0017] In another embodiment, the invention relates to the
separator mentioned above, wherein the size of the DSS particles is
below 250 .mu.m whereby minimizing the cost of the DSS material. It
is to be noticed that larger particles would use more material and
be more expensive for achieving the same effect.
[0018] In another advantageous embodiment, the invention relates to
the separator mentioned above, wherein the thickness of the
separator is ranging from 50 to 1000 .mu.m whereby the dendrite
stopping effect remains. A thicker separator would increase
internal resistivity, would use more material and would be more
expensive, while a thinner separator would have less effect to stop
dendrites.
[0019] The invention also relates to an electrically rechargeable
battery, with strong alkaline electrolyte, comprising at least one
separator according to the invention, as mentioned above, said
separator being placed between a Zinc electrode and a counter
electrode.
[0020] In the invention a "strong alkaline electrolyte" means an
electrolyte having a pH of at least 12.
[0021] In some embodiments the above mentioned battery comprises,
as a cathode, an air electrode.
[0022] Moreover, in some embodiments the above mentioned battery
comprises, as cathode, a nickel-oxide or a silver electrode.
[0023] The present invention provides separators that are
comparatively more resistant to dendrites perforation and provides
battery with longer service life than the one not comprising DSS
particles.
[0024] This invention is advantageously suitable for zinc-nickel,
zinc-silver, zinc-air, lithium-air electrically rechargeable
batteries, especially for their use in stationery applications or
electric vehicles such as e-cars, e-autobuses, e-trucks,
e-bicycles, etc. Thus, the invention also relates to an electric or
hybrid vehicle comprising at least one electrically rechargeable
battery as mentioned above.
[0025] Another aspect of the invention relates to a method for
preparing a separator as defined above, comprising: [0026] a step
of soaking a porous or fibrous material with a DSS precursor, such
as NiCO.sub.3 or NiSO.sub.4 and [0027] a step of having DSS
particles precipitate within the said material.
[0028] According to this process, separator commonly used for
batteries is soaked into a DSS precursor. The DSS material then
precipitates onto the cavities or the pores of the porous or
fibrous material, conferring to the resulting material Dendrite
Stopping properties.
[0029] Another aspect of the invention relates to a method for
manufacturing a separator having Dendrite Stopping properties as
defined above, comprising a step of adding DSS particles into the
mixture of material used to prepare a separator
[0030] This process allows to manufacture a separator that directly
contains DSS particles, and exhibits Dendrite Stopping
properties.
[0031] When preparing such a separator, it is ready to use and does
not need to be soaked with a DSS precursor.
[0032] The invention also relates to the use of a separator as
mentioned above, for manufacturing an electric battery.
[0033] The invention will be further understood from the following
detailed description of specific embodiments. The products and
methods of the invention are illustrated but not limited to the
following examples.
LEGEND TO THE FIGURE
[0034] FIG. 1 shows a cross section view of a zinc-air battery cell
with second reversible electrode and without auxiliary electrode,
where (11) is an air electrode; (12) is a first reversible zinc
electrode; (13) is a second reversible nickel-oxide electrode; (14)
(15) are separators placed in between the neighboring electrodes;
(16) is the casing of the battery.
EXAMPLES
Example 1
[0035] In this first example the inventors prepare a separator
according to the invention by: [0036] adding 7 g of 50-100 .mu.m
Ni(OH).sub.2 particles to 100 ml ethanol C.sub.2H.sub.5OH and
mixing with a magnetic stirrer 20 min. [0037] then 3.3 ml of PTFE
suspension (DuPont.TM. Teflon.RTM. PTFE TE-3893 with particle size
0.05 to 0.5 .mu.m, solid content 60%, density 1.5 g/cc) is added to
the mixture and further mixed for 2 h. [0038] then the mixture is
left to rest and decant. [0039] then the decanted solid mass is
well kneaded and rolled 12 times to obtain separator layers of
thickness down to 0.2 mm. [0040] finally, these separator layers
are dried 48 h at 30.degree. C. during which time the thickness of
the separator increases from 0.2 mm up to 0.25 to 0.3 mm.
[0041] The separator obtained has a very good dendrite stopping
effect.
[0042] It is to be noted that by using Ni(OH).sub.2 particles
smaller than 50 .mu.m thinner layers can be rolled, thus permitting
to obtain a separator final thickness of only 0.1 to 0.15 mm.
Example 2
[0043] In this second example to prepare a separator according to
the invention, the inventors use a microporous PVC separator having
a thickness of 1.1 mm for use in lead-acid batteries manufactured
by Microtex Energy P Ltd., Bengaluru--560058, Karnataka, India.
This material is first soaked during 1 hour with a 200 g/l
NiSO.sub.4 solution (nickel sulfate NiSO.sub.4 is very soluble in
water), then impregnated during 1 hour by strong alkaline solution,
100 g/l KOH, resulting in a precipitation of Ni(OH).sub.2 particles
within the pores of the microporous separator. It is to be noted
that Ni(NO3)2 and NiCl2 could be used instead of NiSO.sub.4 as DSS
precursor, while NaOH, Na.sub.2CO.sub.3 or K2CO3 could be swapped
for KOH. Also the concentrations of both the DSS precursor and
alkaline electrolyte can vary in a range of 35% to 300%.
[0044] Then the separator is well rinsed in water and dried, the
excess of Ni(OH).sub.2 being removed from the separator's surface
mechanically.
[0045] As a result, the in-pore Ni(OH).sub.2 particles could occupy
from 5 to 50% of pore volume with various particle-size
distribution.
[0046] Ni(OH).sub.2 particles are 5 to 10 weight percent from the
final separator's weight.
[0047] Such prepared separator possesses enhanced counter-dendrites
properties.
Example 3
[0048] In this third example one cell zinc-air battery is prepared
including:
[0049] 1--a Zinc anode, an Air-Electrode and an auxiliary electrode
as described in FIG. 2 of WO2013/110097. Briefly, the battery cell
contains the components described below with an additional
indifferent auxiliary electrode made of fine nickel mesh (such as 6
Tyler mesh), it could also be an Ni-coated iron grid, electrically
connected to the nickel-oxide electrode during cell charge.
[0050] A battery cell is prepared, and as shown in FIG. 1 contains
the following components: [0051] an air electrode (11) produced by
the company MEET (Korea, www.mee-t.com); [0052] a zinc electrode
(12), having Ca 5 mm thickness and 5.5 Ah nominal capacity,
prepared for example as described in PCT Application
PCT/AM2010/000001; [0053] a nickel-oxide electrode (13) possessing
1.1 Ah nominal capacity such as one from NKBN 11 D Ni--Cd
accumulator of Lugansk accumulator production plant; all these
electrodes having the same visible surface area of 40.times.80
mm.sup.2;
[0054] 2--a porous separator (14) and (15) according to the
invention (with DSS) used to wrap the Zinc electrode.
[0055] The zinc anode, the separator, the counter electrode and the
air-electrode are bathing, immersed in a strong 6M KOH
electrolyte.
[0056] This battery setup is submitted to cycles of 8 hours 20
mA/cm.sup.2 charging and 6 hours discharging at 25 mA/cm.sup.2.
[0057] At first, a battery comprising the separator as described in
Example 2 is carried out and no dendrite is piercing it after 50
cycles.
[0058] Secondly, a battery comprising the separator used is the
initial PVC microporous separator of example 2, but without the
preparation according to this invention (i.e. without DSS) is
carried out. When used without DSS this separator is pierced by
dendrites after less than 5 cycles at the same charge-discharge
conditions.
[0059] This example shows that the separator of Example 2 possesses
enhanced counter-dendrites properties.
[0060] Specific embodiments of the invention have been described by
the way of exemplary teachings however the scope of the present
invention is not limited to the specific details and the
illustrative examples shown and described. It will be apparent to
persons skilled in the art that modifications and variations can be
made without departing from the scope of the invention.
* * * * *
References